EP3698865A1 - Zéolite contenant de la platine et du manganèse - Google Patents
Zéolite contenant de la platine et du manganèse Download PDFInfo
- Publication number
- EP3698865A1 EP3698865A1 EP19158234.5A EP19158234A EP3698865A1 EP 3698865 A1 EP3698865 A1 EP 3698865A1 EP 19158234 A EP19158234 A EP 19158234A EP 3698865 A1 EP3698865 A1 EP 3698865A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- manganese
- platinum
- zeolite
- metal
- zeolite according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 79
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010457 zeolite Substances 0.000 title claims abstract description 47
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 40
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 35
- 239000011572 manganese Substances 0.000 title claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- GHOKWGTUZJEAQD-ZETCQYMHSA-N (D)-(+)-Pantothenic acid Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCC(O)=O GHOKWGTUZJEAQD-ZETCQYMHSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- -1 platinum cation Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical class [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- IGOJMROYPFZEOR-UHFFFAOYSA-N manganese platinum Chemical compound [Mn].[Pt] IGOJMROYPFZEOR-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/67—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/69—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/743—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/783—CHA-type, e.g. Chabazite, LZ-218
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/2073—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Definitions
- the present invention relates to a platinum- and manganese-containing zeolite and its use as an oxidation catalyst for cleaning the exhaust gases from lean-burn internal combustion engines, in particular diesel engines.
- the raw exhaust gas from diesel engines contains a relatively high oxygen content of up to 15% by volume.
- Particulate emissions are also included, which mainly consist of soot residues and possibly organic agglomerates and result from partially incomplete fuel combustion in the cylinder.
- While diesel particulate filters with and without a catalytically active coating are suitable for removing particulate emissions and nitrogen oxides can be converted to nitrogen, for example by selective catalytic reduction (SCR) on a so-called SCR catalytic converter, carbon monoxide and hydrocarbons are rendered harmless by oxidation on a suitable oxidation catalytic converter made.
- SCR selective catalytic reduction
- oxidation catalytic converters often have the task of setting an optimal ratio of nitrogen monoxide to nitrogen dioxide for an SCR catalytic converter on the downstream side.
- Oxidation catalysts are extensively described in the literature, see for example EP2000639A1 . These are, for example, so-called flow-through substrates made of ceramic or metal, which carry precious metals, such as platinum and palladium, on high-surface, porous, high-melting oxides, for example aluminum oxide, as essential catalytically active components.
- precious metals such as platinum and palladium
- Such catalysts have the disadvantage that they lose activity, especially under lean conditions and at high exhaust gas temperatures. This effect is particularly catalytic on the sintering active precious metals, in particular platinum and palladium, and the associated loss of surface.
- carrier materials such as aluminum oxide also lose their surface with increasing service life. As a result, the conventional oxidation catalytic converters show a considerable difference in performance between the fresh and the aged condition.
- manganese compounds in particular manganese oxide
- catalysts for automobile exhaust gas catalysis are already known, see for example the DE102011109200A1 .
- Manganese oxide MnO 2
- WO2014 / 080220A1 the use of manganese oxide (MnO 2 ) to control sulfur emissions is known.
- Manganese oxide and noble metal are applied to a filter substrate in a coating, although it must be ensured that the noble metal and the manganese oxide are physically separated from each other. This is according to the WO2014 / 080220A1 necessary because the manganese oxide could "poison" the oxidizing ability of the noble metal for hydrocarbons and carbon monoxide.
- the WO2015 / 095056 A1 and WO2015 / 095058 A1 describe catalysts made up of several catalytically active layers, one of these layers containing a manganese-containing carrier oxide for a platinum and optionally a palladium component. In addition to the oxidation of hydrocarbons and carbon monoxide, these catalysts are also able to oxidize nitrogen monoxide to nitrogen dioxide.
- zeolites which contain both platinum and manganese are outstandingly suitable as oxidation catalysts, in particular for the oxidation of nitrogen monoxide to nitrogen dioxide.
- the present invention accordingly relates to a zeolite which comprises manganese and platinum.
- Zeolites are two- or three-dimensional structures, the smallest structures of which are SiO 4 and AlO 4 tetrahedra. These tetrahedra join together to form larger structures, two of which are connected via a common oxygen atom. Rings of different sizes can be formed, for example rings made of four, six or even nine tetrahedrally coordinated silicon or aluminum atoms.
- the different zeolite types are often defined by the largest ring size, because this size determines which guest molecules can penetrate the zeolite structure and which cannot. It is common to differentiate between large-pore zeolites with a maximum ring size of 12, medium-pore zeolites with a maximum ring size of 10 and small-pore zeolites with a maximum ring size of 8. Zeolites are further subdivided by the Structure Commission of the International Zeolite Association into structure types, each of which is assigned a three-letter code, see for Example Atlas of Zeolite Framework Types, Elsevier, 5th Edition, 2001 .
- the zeolite according to the invention can have large, medium or small pores. In other words, it preferably has the largest channels, which are formed by 6, 8, 9, 10 or 12 tetrahedrally coordinated atoms.
- the zeolite according to the invention belongs in particular to the structure type ABW, ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATT, BEA, BIK, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, ESV , ETL, FAU, FER, GIS, GOO, IHW, KFI, LEV, LTA, MER, MFI, MON, MOR, MWW, NSI, OWE, PAU, PHI, RHO, RTH, SAT, SAV, SIV, SOD, STT , THO, TSC, UEI, VNI, YUG or ZON, preferably the structure type AEI, AFT, AFX, BEA, CHA, DDR, ERI, ESV, ETL, FER, KFI, LEV or UFI.
- AEI, AFX, CHA and FER are particularly preferred structure types.
- the zeolite according to the invention has in particular a SAR (silica-to-alumina ratio) value of 2 to 100, in particular of 5 to 50.
- SAR silicon-to-alumina ratio
- zeolite expressly does not include mixed oxides comprising aluminum oxide and silicon oxide, as described in the literature, for example, as “SiO 2 / Al 2 O 3 ”.
- the platinum is preferably present as a platinum cation in the zeolite structure, that is to say in ion-exchanged form. However, it can also be present entirely or partially as platinum metal and / or as platinum oxide in the zeolite structure and / or on the surface of the zeolite structure.
- the platinum can be present in amounts of 0.01 to 20% by weight, based on the sum of the weights of zeolite, manganese and platinum and calculated as manganese metal and platinum metal.
- the platinum is preferably present in amounts from 0.5 to 10, particularly preferably from 0.5 to 6% by weight and very particularly preferably from 0.5 to 5% by weight, based on the sum of the weights of zeolite, Manganese and platinum and calculated as manganese metal and platinum metal.
- the manganese is preferably present as a manganese cation in the zeolite structure, that is to say in ion-exchanged form.
- it can also be wholly or partially present as manganese oxide, in particular as manganese dioxide (MnO 2 ) in the zeolite structure and / or on the surface of the zeolite structure.
- the manganese can be present in amounts of 0.01 to 20% by weight, based on the sum of the weights of zeolite, manganese and platinum and calculated as manganese metal and platinum metal.
- the manganese is preferably present in amounts from 0.5 to 10, particularly preferably from 0.5 to 6% by weight and very particularly preferably from 0.5 to 5% by weight, based on the sum of the weights of zeolite, Manganese and platinum and calculated as manganese metal and platinum metal.
- the zeolite according to the invention preferably has a manganese: platinum mass ratio of 7: 1 to 1:20, platinum being calculated as platinum metal and manganese as manganese metal.
- the zeolite according to the invention can be produced by methods known per se. For example, it is obtained by impregnating a zeolite, for example in the H or Na form, with an aqueous solution of platinum and manganese salts in the appropriate amounts using the incipient wetness method and then drying and calcining.
- Platinum nitrate (Pt [NO 3 ] 2 ) is particularly suitable as the water-soluble platinum salt
- manganese nitrate (Mn [NO 3 ] 2 ) is particularly suitable as the water-soluble manganese salt.
- the impregnated zeolite is calcined in particular at temperatures of 250 to 550.degree.
- the zeolite according to the invention is present on a carrier substrate.
- the present invention also relates to a catalyst comprising a support substrate of length L and a zeolite comprising manganese and platinum.
- the carrier substrate can be a flow-through substrate or a wall-flow filter.
- a wall flow filter is a carrier substrate comprising channels of length L, which extend parallel between a first and a second end of the wall flow filter, which are closed alternately at either the first or second end and which are separated by porous walls.
- a flow-through substrate differs from a wall-flow filter in particular in that the channels of length L are open at both ends.
- wall-flow filters In the uncoated state, wall-flow filters have, for example, porosities of 30 to 80, in particular 50 to 75%. Their average pore diameter in the uncoated state is, for example, 5 to 30 micrometers.
- the pores of the wall flow filter are so-called open pores, i.e. they are connected to the channels. Furthermore, the pores are usually connected to one another. On the one hand, this enables light coating of the inner pore surfaces and, on the other hand, a light passage of the exhaust gas through the porous walls of the wall flow filter.
- Flow-through substrates like wall-flow filters, are known to the person skilled in the art and are available on the market. They consist, for example, of silicon carbide, aluminum titanate or cordierite.
- the zeolite which comprises manganese and platinum, is present in the form of a coating on the carrier substrate.
- the coating can extend over the entire length L of the carrier substrate or only over part of it. In both cases, the carrier substrate can also have one or more further catalytically active coatings.
- the coating can be on the surfaces of the inlet channels, on the surfaces of the outlet channels and / or in the porous wall between inlet and outlet channels.
- Catalysts according to the invention in which the zeolite, which comprises manganese and platinum, are present in the form of a coating on the carrier substrate, can be produced by methods familiar to the person skilled in the art, for example by the usual dip coating processes or pump and suction coating processes with subsequent thermal Post-treatment (calcination).
- the person skilled in the art is aware that in the case of wall flow filters, their average pore size and the average particle size of the materials to be coated can be matched to one another in such a way that they lie on the porous walls that form the channels of the wall flow filter (on-wall coating).
- the mean particle size of the materials to be coated can, however, also be selected so that they are located in the porous walls that form the channels of the wall flow filter, so that the inner pore surfaces are coated (in-wall coating). In this case the mean particle size of the materials to be coated must be small enough to penetrate into the pores of the wall flow filter.
- the carrier substrate is formed from the zeolite, which comprises manganese and platinum, and a matrix component.
- Carrier substrates, flow-through substrates, as well as wall-flow filters, which not only consist of inert material such as cordierite, but also contain a catalytically active material, are known to the person skilled in the art. To produce them, a mixture of, for example, 10 to 95% by weight of inert matrix component and 5 to 90% by weight of catalytically active material is extruded using processes known per se. All inert materials that are otherwise used for the production of catalyst substrates can be used as matrix components.
- extruded carrier substrate which comprises the zeolite, the manganese and platinum, can in embodiments of the present invention be coated with one or more catalytically active coatings.
- a carrier substrate which is constructed from corrugated sheets of inert materials.
- carrier substrates are known to the person skilled in the art as "corrugated substrates".
- Suitable inert materials are, for example, fibrous materials with an average fiber diameter of 50 to 250 ⁇ m and an average fiber length of 2 to 30 mm. Fibrous materials are preferably heat-resistant and consist of silicon dioxide, in particular of glass fibers.
- sheets made of the fiber materials mentioned are corrugated in a known manner and the individual corrugated sheets are shaped into a cylindrical monolithically structured body with channels running through the body.
- a monolithically structured body is formed with a criss-cross corrugation structure.
- non-corrugated, ie flat, sheets can be arranged between the corrugated sheets.
- Corrugated sheet substrates can be coated directly with the zeolite, which comprises manganese and platinum, but are preferably coated first with an inert material, for example titanium dioxide, and only then coated with the catalytic material.
- the catalyst according to the invention is outstandingly suitable as an oxidation catalyst for the treatment of exhaust gas from lean-burn internal combustion engines. It is suitable for the oxidation of hydrocarbons and carbon monoxide, but especially for the oxidation of nitrogen monoxide to nitrogen dioxide.
- the difference between its activity in the fresh and in the aged state is significantly smaller than in the case of oxidation catalysts that have been used up to now, for example, comprising platinum supported on aluminum oxide.
- the catalyst obtained is called K1 below.
- Example 1 is repeated with the difference that the amount of manganese is 4% by weight.
- the catalyst obtained is called K2 below.
- Example 1 is repeated with the difference that the amount of manganese is 5% by weight.
- the catalyst obtained is called K3 below.
- Example 1 is repeated with the difference that the amount of manganese is 7% by weight.
- the catalyst obtained is called K4 below.
- the catalyst obtained is called K5 below.
- Example 1 is repeated with the difference that no manganese is used.
- the catalyst obtained is referred to below as VK1.
- Example 5 is repeated with the difference that no manganese is used.
- the catalyst obtained is referred to below as VK2.
- Pt and Pd nitrate are placed in water in a ratio of 6: 1 and an aluminum oxide is added so that the final total precious metal concentration in the washcoat is 0.94%.
- a ceramic carrier is coated as described in Example 1. The The final temperature treatment in air includes drying at 120 ° C and calcination and tempering at 350 ° C.
- the catalyst obtained is referred to below as VK3.
- a synthetic test exhaust gas consisting of 10% O 2 , 7.5% H 2 O, 7% CO 2 , 250 ppm CO, 750 ppm NO, remainder N 2 at 1950 L / hour was passed through the drill cores obtained according to a) in a laboratory reactor .
- the temperature of the test exhaust gas was increased at 15 ° C / min from 75 ° C to 500 ° C and the NO conversion was determined using a conventional method.
- the Figures 1 to 9 show that the inventive catalysts K1 to K5 are significantly more stable to aging.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19158234.5A EP3698865A1 (fr) | 2019-02-20 | 2019-02-20 | Zéolite contenant de la platine et du manganèse |
CN202080006397.9A CN113164870A (zh) | 2019-02-20 | 2020-02-20 | 含有铂和猛的沸石 |
PCT/EP2020/054412 WO2020169697A1 (fr) | 2019-02-20 | 2020-02-20 | Zéolithe contenant du platine et du manganèse |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP19158234.5A EP3698865A1 (fr) | 2019-02-20 | 2019-02-20 | Zéolite contenant de la platine et du manganèse |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3698865A1 true EP3698865A1 (fr) | 2020-08-26 |
Family
ID=65529361
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19158234.5A Pending EP3698865A1 (fr) | 2019-02-20 | 2019-02-20 | Zéolite contenant de la platine et du manganèse |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3698865A1 (fr) |
CN (1) | CN113164870A (fr) |
WO (1) | WO2020169697A1 (fr) |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3329604A (en) * | 1964-02-21 | 1967-07-04 | Exxon Research Engineering Co | Hydrocarbon conversion catalysts containing a manganese promoter on a crystalline zeolite for the hydrocracking of hydrocarbons |
EP0186399A2 (fr) * | 1984-12-28 | 1986-07-02 | Mobil Oil Corporation | Procédé et catalyseur pour la conversion de propane en propylène |
EP0491360A1 (fr) * | 1990-12-18 | 1992-06-24 | Tosoh Corporation | Catalyseur pour la purification des effluents gazeux |
JP2007144278A (ja) * | 2005-11-25 | 2007-06-14 | Mitsubishi Electric Corp | 脱臭装置およびそれを備えた空気調和装置 |
EP2000639A1 (fr) | 2006-03-30 | 2008-12-10 | ICT Co., Ltd. | Procede de purification de gaz d'echappement provenant de moteur a combustion interne |
DE102011109200A1 (de) | 2010-08-10 | 2012-02-16 | Gm Global Technology Operations Llc (N.D.Ges.D. Staates Delaware) | Grundmetalloxid-Oxidationskatalysator |
WO2014080220A1 (fr) | 2012-11-22 | 2014-05-30 | Johnson Matthey Public Limited Company | Catalyseur zoné sur un substrat monolithique |
WO2015095058A1 (fr) | 2013-12-16 | 2015-06-25 | Basf Corporation | Catalyseur d'oxydation contenant du manganèse pour moteur diesel |
WO2015095056A1 (fr) | 2013-12-16 | 2015-06-25 | Basf Corporation | Catalyseur d'oxydation diesel contenant du manganèse |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DK1129764T3 (da) * | 2000-03-01 | 2006-01-23 | Umicore Ag & Co Kg | Katalysator til rensning af udstödningsgas fra dieselmotorer og fremgangsmåde til dens fremstilling |
BR112013031349A2 (pt) * | 2011-06-05 | 2016-11-29 | Johnson Matthey Plc | catalisador, artigo catalisador, método para tratar emissões, e, sistema para tratar gás de escape |
GB201401115D0 (en) | 2014-01-23 | 2014-03-12 | Johnson Matthey Plc | Diesel oxidation catalyst and exhaust system |
GB201405868D0 (en) * | 2014-04-01 | 2014-05-14 | Johnson Matthey Plc | Diesel oxidation catalyst with NOx adsorber activity |
-
2019
- 2019-02-20 EP EP19158234.5A patent/EP3698865A1/fr active Pending
-
2020
- 2020-02-20 WO PCT/EP2020/054412 patent/WO2020169697A1/fr active Application Filing
- 2020-02-20 CN CN202080006397.9A patent/CN113164870A/zh active Pending
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3329604A (en) * | 1964-02-21 | 1967-07-04 | Exxon Research Engineering Co | Hydrocarbon conversion catalysts containing a manganese promoter on a crystalline zeolite for the hydrocracking of hydrocarbons |
EP0186399A2 (fr) * | 1984-12-28 | 1986-07-02 | Mobil Oil Corporation | Procédé et catalyseur pour la conversion de propane en propylène |
EP0491360A1 (fr) * | 1990-12-18 | 1992-06-24 | Tosoh Corporation | Catalyseur pour la purification des effluents gazeux |
JP2007144278A (ja) * | 2005-11-25 | 2007-06-14 | Mitsubishi Electric Corp | 脱臭装置およびそれを備えた空気調和装置 |
EP2000639A1 (fr) | 2006-03-30 | 2008-12-10 | ICT Co., Ltd. | Procede de purification de gaz d'echappement provenant de moteur a combustion interne |
DE102011109200A1 (de) | 2010-08-10 | 2012-02-16 | Gm Global Technology Operations Llc (N.D.Ges.D. Staates Delaware) | Grundmetalloxid-Oxidationskatalysator |
WO2014080220A1 (fr) | 2012-11-22 | 2014-05-30 | Johnson Matthey Public Limited Company | Catalyseur zoné sur un substrat monolithique |
WO2015095058A1 (fr) | 2013-12-16 | 2015-06-25 | Basf Corporation | Catalyseur d'oxydation contenant du manganèse pour moteur diesel |
WO2015095056A1 (fr) | 2013-12-16 | 2015-06-25 | Basf Corporation | Catalyseur d'oxydation diesel contenant du manganèse |
Also Published As
Publication number | Publication date |
---|---|
CN113164870A (zh) | 2021-07-23 |
WO2020169697A1 (fr) | 2020-08-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102015100984B4 (de) | Abgassystem mit Dieseloxidationskatalysator | |
DE102015112465B4 (de) | System und verfahren zum behandeln von abgas | |
EP2718011B1 (fr) | Procédé pour la réduction catalytique sélective d'oxydes d'azote dans les gaz d'échappement de moteurs diesel | |
DE102016111150A1 (de) | Ammoniak-Sperrkatalysator mit geringer N2O-Bildung | |
DE102016111147A1 (de) | Abgassystem ohne einen DOC, das einen als einen DOC wirkenden ASC in einem System mit einem SCR-Katalysator vor dem ASC aufweist | |
DE102016118542A1 (de) | Einen russkatalysator und einen scr-katalysator aufweisendes katalytisches filter | |
DE102016111148A1 (de) | Ammoniak-Sperrkatalysator, ausgestaltet um der Erste in einem SCR-System zu sein | |
DE102016111151A1 (de) | Einzel- oder doppelschicht-ammoniaksperrkatalysator | |
DE102015212356A1 (de) | Perowskit mit einer Deckschicht-SCR-Komponente als Ammoniakoxidationskatalysator und System zur Abgasreinigung bei Dieselmotoren | |
DE102016111000A1 (de) | Gegen NH3-Überdosierung toleranter SCR-Katalysator | |
DE102015209987A1 (de) | Nicht-PGM-Ammoniakschlupfkatalysator | |
DE102016110999A1 (de) | Zoniertes Abgassystem | |
DE102015105029A1 (de) | Diesel oxidation catalyst with nox adsorber activity | |
DE102015119913A1 (de) | Kombination von SCR mit PNA zur Niedrigtemperaturemissionssteuerung | |
DE102015107647A1 (de) | Katalytischer Gegenstand zum Behandeln vom Abgas | |
EP2335810A1 (fr) | Réduction catalytique sélective d'oxydes d'azote dans du gaz d'échappement de moteurs diesel | |
DE102017122001A1 (de) | Ruthenium, geträgert auf trägern, die eine rutilphase aufweisen, als stabile katalysatoren für nh3-slip-anwendungen | |
DE102017120303A1 (de) | DIESELOXIDATIONSKATALYSATOR MIT NOx-ADSORBERAKTIVITÄT | |
WO2018054928A1 (fr) | Filtre à particules pourvu d'un revêtement à effet de réduction catalytique sélective | |
DE102016102527A1 (de) | Katalysator mit stabiler Stickstoffmonoxid(NO)-Oxidationsleistung | |
EP3496852B1 (fr) | Materiau scr actif | |
EP3592458B1 (fr) | Catalyseur diesel à oxydation contenant du manganèse | |
DE202008018318U1 (de) | Kupfer-Cha-Zeolith-Katalysatoren | |
EP3885040A1 (fr) | Catalyseur d'oxydation d'ammoniac | |
EP3698865A1 (fr) | Zéolite contenant de la platine et du manganèse |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210226 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20230825 |
|
RAP3 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UMICORE AG & CO. KG |